Chemical Engtne~ring Thence. Vol. 45. No 2. pp. 553-559. 1990 coo%2So9/w 33.00 + 0.

00
Printed m Great Britain. C 1990 Pcrgamon Press plc

DIGITAL SIMULATION OF INDUSTRIAL FLUID

CATALYTIC CRACKING UNITS: BIFURCATION AND ITS
IMPLICATIONS

S. S. ELSHISHINI
Chemical Engineering Department, College of Engineering, Cairo University, Cairo, Egypt

and

S. S. E. H. ELNASHAIE+
Chemical Engineering Department, College of Engineering, King Saud University, Riyadh, PO Box 800,
Saudi Arabia

(Firs received 16 October 1988; accepted in revised form 9 June 1989)

Abstract-The mathematical model for fluid catalytic cracking units developed earlier (Elnashaie, S. S. E. H.
and El-Hennawi, I. M., 1979, Chem. Engng Sci. 34, 1113-1121) has been used, after introducing some
modifications, to simulate two industrial units. The model results were found to be in good agreement with
the plant data. It was found that the plants operate at the middle unstable steady state and that the yield can
be increased to its maximum value by manipulating some of the operating variables. A parametric study has
been conducted to investigate the effect of some parameters on the operating middle steady states,
bifurcation behaviour and gasoline yield.

INTRODUCTION Six years later, Elnashaie and El-Hennawi (1979)

Fluid catalytic cracking (FCC) is one of the developed a relatively more rigorous model using the
important industrial processes that prove the great three pseudo-components kinetic model of Weekman
practical importance of the extensive work done on (1968) and taking into consideration the two-phase
the multiplicity of steady states in chemical reactors nature of both fluidized beds in the reactor and the
[Luss and Amundson (1968), Villadsen and Michelsen regenerator. They concluded from an extensive para-
(1972), Uppal et al. (1976), Elnashaie (1977), metric investigation that the multiplicity phenomenon
Balakotaiah and Luss (1982) and Farr and Aris (1986), existed over a very wide range of parameters and
to mention just a fen]. that FCC units are usually operating at the middle
Awareness of the problem of the multiplicity of unstable steady state.
steady states in FCC units was started almost 20 years Very recently Edwards and Kim (1988) observed
ago by a very interesting paper (Iscol, 1970) in which multiplicity of the steady state for a commercial FCC
the author tried to explain the continuous drift in the unit and used a simple empirical model to verify the
operation of a commercial FCC unit using a very existence of this multiplicity region.
simple, almost empirical model, and showed that the The models of Iscol (1970), Lee and Kugelman
unit is operating in the multiplicity region and specifi- (1973) and Edwards and Kim (1988) are not only
cally at the middle unstable steady state, and that mostly empirical but they also do not involve any
because of the very high capacity of the system the reaction network, and therefore the implications of the
instability of this middle steady state manifests itself as bifurcation behaviour of the unit on gasoline yield was
a relatively slow drift from the operating unstable not investigated.
steady state. The present paper is aiming at introducing some
About 3 years later Lee and Kugelman (1973) modifications into the relatively rigorous model devel-
developed a model which was restricted with too oped earlier by Elnashaie and El-Hennawi (1979) and
many assumptions, and concluded from their in- then using the model to simulate two commercial
vestigation that multiplicity of the steady states does FCC units and to investigate the bifurcation behav-
not exist for realistic values of the parameters. iour of the unit and its implications on gasoline yield.

KINETICS AND THERMOCHEMISTRY OF CRACKING AND

COKING REACTIONS

‘Author to whom all correspondence should be addressed. The reaction network, kinetic rate constants and
On leave from the Chemical Engineering Department, Cairo heats of reaction are given below (Weekman, 1968,
University, Cairo, Egypt. 1969; Weekman and Nate, 1970; El-Hennawi, 1977):

553
 554 S. S. ELSHISHINI and S. S. E. H. ELNASHAIE

Gas oil A gasoline *2 coke + gases

k,
f

k, = 4.468 exp( - 20,833.3/RT)m3/kgs AH, = 601.92 kJ/kg

k, = 10,773.5 exp ( - 75,240/R T) t/s AH, = 7524 kJ/kg
k, = 17.092 exp( - 37,620/RT)m3/kgs AH, = 8125.92 kJ/kg.

The simple coke burning rate (Kunii and Levenspiel,

1969, pp. 482,518; Levenspiel, 1962, p. 356) is used. It to CO and the combustion of hydrogen. The volu-
is given by metric gas flow rate at outlet is thus

C, = K,(l - x,)C, kg coke burned/kg solid s RCDRTG FAR TG

G, = (0.5 P, + 0.5 P,,) +p
(1) loop, 29P,
K, = 1.6821 x lo* exp (- 118,895.9/RT,) where P, = wt % of hydrogen in coke, P, = vol % of
m3/kmol s. CO to (CO + CO,) in flue gases, and R,, = amount
The heat of combustion of coke is calculated from the of coke formed (kg/s). For the reactor the volumetric
correlation (Nelson, 1964, p. 789): flow rate at outlet is given by

1
(- AH,) = [4100 + f0,100(CO,/CO, + CO) (1 -x1 -x,)(1 - CORR)
+ 3370(H/C)] x 2.326 kJ/kg MG

where CO,/(CO, + CO) refers to the relative volume FGR TR

of these gases in the flue gas, and H/C to the atomic
ratio of hydrogen to carbon in coke. Heat losses in the
xp,
reactor were assumed to be 0.5% of the heat entering where M,,, M,, and M, are the molecular weights of
with the catalyst, and the heat losses in the regenerator gas oil, gasoline and gases. CORR is the weight
were assumed to be 0.5% of the heat supplied by coke fraction of coke/(coke + gases).
burning. The rest of the data are given in the (2) The heats of cracking of El-Hennawi (1977) are
Appendix. overestimated and, in the simulation study, they had
to be multiplied by a factor of 0.33. This is due to the
fact that gas oil and gasoline crack to coke and lighter
HYDRODYNAMIC AND PHYSICAL PARAMETERS
hydrocarbons while the heats of cracking of El-
The calculation of the hydrodynamic parameters Hennawi are based on complete cracking to coke and
for the two-phase model of fluidized beds is based on hydrogen. These modified heats of cracking give an
the simple model of Kunii and Levenspiel (1969, pp. overall heat of cracking which is very close to the
13&133) with the following assumptions: emperical values used industrially (Nelson, 1964,
p. 795; Shell, 1975; Elnashaie and Elshishini, 1984).
(1) There is no reaction in the bubble phase. (3) The amount of light hydrocarbons is calculated
(2) The dense phase is perfectly mixed and the from the weight ratio of coke to (coke + gases) given
bubble phase is in plug flow with respect to mass in plant data.
and heat. (4) The Weekman kinetic scheme does not account
(3) Interchange between bubble phase gas and for the formation of HCO (heavy cycle oil), CSO
dense-phase gas is by bulk flow and diffusion. (clarified oil) and LCO (light cycle oil), which are the
(4) An average mean bubble diameter is used fractions produced from the cracking of gas oil. The
throughout the bed. only fraction recycled is HCO and, to calculate it, the
(5) Heats of reaction and physical properties are ratio HCO/(HCO + LCO + CSO) has to be obtained
constant except for diffusivities, density of from plant data.
vaporized gas oil, and density of air, which are
functions of temperature. PLANT DATA

(6) Excess air is used in the regenerator. The two industrial fluid catalytic crackers con-
sidered are of the model IV type (with U-bends). The
MODEL DEVELOPMENT two units vary in input parameters which lead to
The modeldeveloped earlier by Elnashaie and El- different output parameters. Table 1 gives the plant
Hennawi (1979) is used after introducing the following data for the two commercial FCC units. Additional
modifications into it: plant data common to both units are given in Table 2.

(1) The volumetric gas flow rates in regenerator and SIMULATION PROCEDURE

reactor are taken as the average between the inlet and The model was fitted to the first FCC unit using
outlet values. In the regenerator, the increase in the correction factors for the frequency factors. The modi-
number of moles is due to incomplete oombustion of C fied frequency factors k’,,, = l.Sk,,, k;, = OSk,,, k;,
 Digital simulation of industrial fluid catalytic cracking units 555

Table 1. Plant data for both units

Unit 1 Unit 2

Fresh feed (kg/s) 16.782 13.476

Recycled HCO (kg/s) 2.108 2.111
Combined feed ratio (CFR) 1.1256 1.1566
Air flow rate (kg/s) 10.670 10.670
Catalyst circulation rate (kg/s) 88.605 117.113
Combined feed temperature (K) 527 538
Air feed temperature (K) 436 433
Hydrogen in coke (wt %) 4.17 6.79
HCO/(HCO + CSO + LCO) 0.286 0.419
Coke/coke + gases 0.221 0.207
CO,/(COz + CO) (m3/mJ) 0.75 0.613
(- AH,) (kJ/W 31,235.6 30,776.5

Table 2. Plant data common to both units

Regenerator dimensions 5.334 m ID x 14.859 m TT

Reactor dimensions 3.048 m ID x 12.760 m TT
Catalyst retention in reactor 17.5 metric tons
Catalyst retention in regenerator 50 metric tons
API of raw oil feed 28.7
Reactor pressure 225.4938kPa
Regenerator pressure 254.8708 kPa
Average particle size 0.00072 m
Pore volume of catalyst 0.0003 1 m3/kg
Apparent bulk density 800 kg/m3
Catalyst surface area 215 m’/g

2.5 k,,. Of course, these correction factors will vary
fyom one catalyst to another, depending upon the type
of catalyst, its activity, age and the type of feedstock
used as well as the combined feed ratio (Farag and
Tsai, 1987). To make sure that these correction factors
are not just empirical numbers that fit only this
FCC unit at these specific operating conditions, the
model, with the correction factors, has been used
without any modifications to simulate the second
FCC unit which has a very similar catalyst with
almost the same activity and age and a very similar
feedstock.
The success of this second simulation ensures to a
large extent that the developed model is a reasonably
general representation of these FCC units. However,
the catalyst activity should be regularly checked to
ensure the validity of the pre-exponential factors used
in the simulation.
RESULTS AND DISCUSSION
Comparison of model results with plant data
Figure l(a) shows the heat function vs reactor tem-
perature for units 1 and 2 and Fig. l(b) shows the
corresponding unreacted gas oil (x1) and gasoline
yield (x2). Table 3 gives the values of the output
variables obtained from the model results and from
plant data for units 1 and 2. It is clear that the
agreement is quite good.
The simulation can be improved if more accurate
kinetic data are provided for the same kinetic scheme
and can be improved further if the kinetic scheme was
extended to include separate routes for the formation
of coke and light gases.
It is clear from Table 3 and Fig. l(a) and (b) that
both units are operating at the middle unstable steady
state and both are not operating at their maximum
gasoline yield.
Parametric study
The units being operated at the middle unstable
steady state, it is expected that the steady-state re-
sponse of the system to variation in operating con-
ditions will be somewhat unusual as has been shown
previously (Elnashaie et al., 1972; Elnashaie and El-
Bialy, 1980) for a much simpler system. Therefore, a
detailed parametric investigation of the unit was
carried out using the present model, in order to gain a
deeper insight info the behaviour of this rather com-
plex system. It is obvious that the optimization prob-
lem in the neighbourhood of the unstable middle
steady state will be different from that in the neigh-
bourhood of the stable high-temperature steady state.
There will also be an obvious trading between the
gasoline yield of the system and its stability, i.e., in
some cases, higher yields correspond to an operating
point closer to the critical bifurcation point.
The parametric study is simplified by the fact that
the x1, x2 vs Y diagrams do not change with variations
in F,, YfO or Ylc; the only changes being in the
operating temperatures of the reactor and regener-
ator. For any operating temperature the correspond-
ing x1 and x2 can be obtained from the same curves
[Fig. l(b)]. The parametric investigation presented
here will be confined to FCC unit 1 with its xl, x2 vs Y
diagram shown in Fig. l(b).
 556 S. S. ELSHISHINI and S. S. E. H. ELNASHAIE

in a forthcoming paper dealing with the control

INDUSTRIAL UNIT 1 strategies for these units.
---- lND”STRlAL UNIT 2

5 2.0-
EfSects of gas oilfeed temperature. Figure 2(b) shows
k that for the middle steady state the increase in the gas
x
oil feed temperature (Y,,) from 450 to 527 to 539 K
causes the dimensionless reactor temperature to de-
crease from I.76 to 1.56 to 1.07. This increase in YIG
causes a decrease in conversion and an increase in
gasoline yield (x2) from 0.314, to 0.3857 to 0.3971
[Fig. l(b)]. The opposite response of the middle steady
state compared to the response of the other steady
Vaporization t*mp states is again evident.
ot 90s oil

4.C)-

INDUSTAIAC UNIT 1

0.80

I-\ ---- INDUSTRIAL UNIT 2

2.CI-

0.c )-

- 2.1Il-

Vaporization temp.
- 4.t .
0.00 1.00 2.00 3.00 4.c:-
-.-.- TtG : 450 ‘K
D1MENSIONLESS REACTOR TEMPERATURE(Y)
----- TtG = 527 OK
_ T,G = 539 ‘K
Fig. 1. (a) Heat function for units 1 and 2; (b) conversion and 2.CI-
gasoline yield for units 1 and 2.

0.CI-
Effect of catalyst circulation rate. Figure 2(a) shows
that, for the middle steady state, the reactor temper-
ature (Y) decreases from 1.75 to 1.56 to 1.5 as the
catalyst circulation rate (F,) increases from 44.302 to - 2.t I-
88.605 to 177.21 kg/s. The corresponding conversion
(1 - x1) decreases while the corresponding gasoline
Vaporization tcmp-of gas oil
yield (x2) increases from 0.314 to 0.385 to 0.41 - 4.1 I_ I/- l I
[Fig. l(b)]. It is clear from Fig. 2(a) and (b) that the 0.00 1.00 2.00 3.00 4.00
response of the middle steady state to the change in DIMENSIONLESS REACTOR TEMPERATURE(Y)
any parameter is opposite to the response of the other
steady states (Elnashaie et al., 1972). This fact is of Fig. 2. (a) Effect of catalyst circulation rate on heat function
great importance with respect to the optimization and for unit 1; (b) effect of gas oil feed temperature on heat
control of FCC units and will be discussed in full detail function for unit 1.

Table 3. Simulation of FCC units 1 and 2

Model results Plant data % error

Parameter Unit 1 Unit 2 Unit 1 Unit 2 Unit 1 Unit 2

Y 1.55 1.57 1.55 1.57 0 0

YG 1.98 1.85 1.9 1.88 + 4.21 - 1.6
Xl 0.382 0.355 0.39 0.322 - 2.05 + 10.25
%ke 4.2
0.39 0.39
4.083 0.415
3.681 0.4 1
4.073 -+ 14.1
6.02 -+ 0.25
4.9
(kg/s)
HCO (kg/s) 2.057 2.354 2.109 2.111 - 2.45 -11.6
 Digital simulation
Bifurcation diagrams
It is clear from the previous results that the reactor
is not operated at the optimum operating conditions.
These optimum operating conditions cannot be esti-
mated unless the multiplicity regions are specified for
different parameters, because as the system ap-
proaches maximum yield it gets closer to the bifurca-
tion point where ignition of the reactor can occur.
To obtain the reactor temperature at the different
steady states, the bisectional method was used to solve
the heat balance equation.
Efict ofF, on the bifurcation behaviour. Figure 3(a)
shows the bifurcation diagram for three different
values of the catalyst circulation rate (F,): 177.21,
88.605 and 44.303 kg/s. The multiplicity region in-
creases as F, decreases. As the air temperature increas-
es, the yield corresponding to the middle steady state
increases [Fig. 3(b)]. However, the system is ap-
of industrial fluid catalytic cracking units 551
proaching the bifurcation point and at an air temper-
ature higher than 1.7 (for the case of E; = 44.302),
ignition occurs, i.e. the reactor operates at the high-
temperature steady state to which corresponds a
negligible gasoline yield represented by the lower
branch of the bifurcation diagram [Fig. 3(b)]. At
higher circulation rates, the drop in gasoline yield
occurs at Y,, = 1.65 for F, = 88.605 and Y,, = 1.6 for
F, = 177.21.
The plant is operated at F, = 88.605 and Y,,
= 0.875 (with a gasoline yield of 0.39) which means
that a higher yield can be obtained either by increasing
F, or increasing the air feed temperature. The
optimum yield occurs at Y,-. = 1.5 for F, = 88.605 and
Y,U = 1.46 for F, = 177.21. For F, = 44.302 the high-
est yield is at Y,-, = 1.7 but this corresponds to the
bifurcation point above which ignition occurs. A
gasoline yield of 0.47 (20% improvement) can be
achieved by increasing both F, and air temperature.

4.0
-.-,- Da = 0.1 m
---- 0;~ 0.2m

_---

Fc z88.605 kg/s
2

(a)
L I

_.-.- gE,= 44.302 lag IS

__--- Fe = 86,605 kg/s
-F,: 177.210 kgls

-.-.- 0 8’ 0.1 m
---_ Dg = 0.2 m
- De = 0.3m

3 (b)
F, ~88.605 kg Is
(d)

.--.-.
- --_-‘=-_~~-_.,._.~.-._.,
-6,
I

0.00 1.00 2.00 3.0 0 1.00 2.00 3.00

DIMENSIONLESS AIR FEED TEMPERATURE(Yf,)

Fig. 3. (a) Effect of catalyst circulation rate on the bifurcation diagram of Y vs Y,,; (b) effect of catalyst
circulation rate on the bifurcation diagram of X, vs Y,,; (c)effect of D, on the bifurcation diagram of Y, vs
Y,,; (d) effect of D, on the bifurcation diagram of X,, vs Y,, (1 = low-temperature steady state, 2 = middle
steady state, 3 = high-temperature steady state).
558 S. S. ELSHISHINI and S. S. E. H. ELNASHAIE

Efict of Da on the bf&rcation behaviour. In the conditions of maximum gasoline yield and suggestions
developed model the bubble diameter was taken as a have been given to improve the gasoline yield without
constant value throughout the bed and is calculated getting into a formal optimization investigation yet.
from (Fryer and Potter, 1972)

D,=
(u - Um,)ffm,
(H - H,,)0.711 gi” 1’ cso
NOTATION

clarified oil, kg/s

concentration of oxygen, gas oil and
Ch CA,, CA2

and was found to be 0.1 m. For this bubble diameter gasoline, respectively, in output
(and smaller) the dense-phase conditions and the stream, kg/m3
conditions at the exit of the bubble phase are quite concentration of gas oil and gasoline,
close. However, for larger bubble diameters, the dif- respectively, in the dense phase of the
ference is appreciable. The effect of bubble diameter reactor, kg/m3
on bifurcation is investigated to measure the sensit- c Al/V C.42, concentration of gas oil and gasoline,
ivity of the system to bubble diameter and the pos- respectively, in input stream, kg/m3
sible need to incorporate more rigorous means of CFR combined feed ratio, total feed/fresh
calculating an average value for the bubble diameter feed
or the need to take bubble size variation along the DL? bubble diameter, m
height of the reactor. Figure 3(c) and (d) show the HCO heavy cycle oil, kg/s
bifurcation diagrams for the dense phase for different H, H,, bed height (expanded and at mini-
average bubble sizes. Figure 3(c) shows the increase in mum fluidization), m
the range of the multiplicity region as D, increases KC rate constant for coke combustion re-
whereas Fig. 3(d) shows the corresponding gasoline action, m3/kmol s
yield. It is clear that the system is quite sensitive to K,, K,, K, rate constants for reactions 1
bubble diameter. For the middle steady state, as D, (m3/kg s), 2 (l/s) and 3 (m3/kgs)
increases from 0.1 to 0.2 the gasoline yield in the dense LCO light cycle oil, kg/s
phase increases also, but a further increase to D, = 0.3 Rc coke make rate (@[a,~: exp
causes a decrease in the dense-phase gasoline yield. ( - ~4 Y) + azX2 exp ( - r2l VII
For the high-temperature steady state as D, increases gas constant, kJ/kgmol K
xZD decreases. The effect of D, on the bifurcation reactor dense phase temperature, K
behaviour based on the exit reactor conditions (dense air and gas oil feed temperature, re-
phase + bubble phase) is quite complex and will be spectively, K
discussed in a forthcoming paper dealing entirely with reactor and regenerator temperature,
the effect of hydrodynamic parameters on the per- respectively, K
formance of FCC units. T,,, To reference temperature and gas oil
An improvement in the model simulation of the vaporization temperature, respect-
industrial units can be achieved by obtaining a more ively, K
accurate experimental estimate of the average bubble u superficial gas velocity in the bed, m/s
size. Taking into consideration bubble variation along u m/ minimum fluidization velocity, m/s
the height of the bed will complicate the model Xl, X2 exit dimensionless concentration of
considerably and is not expected to affect the predic- gas oil and gasoline (x, = CR,/CA,/,
tion of the model in comparison with a model using a X 2 = CAZICAl/~
good estimate of constant average bubble size (Fryer XlDI XZD dimensionless reactor concentrations
and Potter, 1972). of gas oil and gasoline, respectively, in
dense phase
Xl/Y x2.f dimensionless concentration of gas
oil and gasoline in the feed
CONCLUSIONS
XL3 amount of coke burnt/total amount of
The model developed has proved to simulate the coke
industrial data quite well. It was found that the reactor y, y, exit reactor and regenerator dimen-
is operated at the middle unstable steady state for both sionless temperature, respectively (Y
industrial FCC units investigated. The verified model = T.sIT,/, YG = TG/TrI)
has been used in a parametric investigation that has YD reactor dense phase dimensionless
shown that the response of the middle steady state to temperature (TJT,,)
variation in the input parameters is opposite to that of y/mY” dimensionless air feed temperature
the high-temperature steady state. The bifurcation and gas oil vaporization temperature,
investigation has shown that the multiplicity region is respectively
quite large and has uncovered the regions of sensitivity heat of reaction for the cracking reac-
near the bifurcation points. It has been shown that the tions, kJ/kg
commercial units are not operating at their optimum heat of combustion of coke, kJ/kg
 Digital simulation of industrial fluid catalytic cracking units 559

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New York.
Balakotaiah, V. and Luss, D., 1982, Structure of the steady
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APPENDIX
Farr, W. W. and Aris, R., 1986, Yet who would have thought
the old man to have so much blood in him? Reflections on Average molecular weight of gas oil = 180
the multiplicity of the steady state of stirred tank reactors. Boiling point of gas oil = 539 K
Chem. Engng Sci. 41, 1385-1402. Average molecular weight of gasoline = 110
Fryer, C. and Potter, 0. E., 1972, Bubble size variation in Boiling point of gasoline = 411 K
two-phase models of fluidized bed reactors. Pow&i Latent heat of vaporization of gas oil = 265.15 kJ/kg
Technol. 6, 3 17-322. T,/ = 500 K, C,,, = 0
Iscol, L., 1970, The dynamics and stability of a fluid catalytic Voidage in both vessels = 0.4
cracker. Joint Automatic Control Conference, Atlanta, Height of expanded bed in
Georgia, pp. 602-607. reactor (H,) = 7 m under the operating
Kunii, D. and Levenspiel, O., 1969, Fluidiration Engineering. Height of expanded bed in conditions of unit 1
Wiley, New York. regenerator (HG) = 7.2 m